Light-sensitive silver halide color photographic material containing cyancolored couplers

ABSTRACT

WHEREIN N IS AN INTEGER OF 1 TO 4; M IS AN INTEGER OF 0 TO 2; R is a phenyl group or an alicyclic group, may be used in the form of a solution in an organic solvent which has an automasking mechanism for compensating the drawback in color reproduction of the light-sensitive, silver halide, color photographic material, said cyan-colored coupler having such properties as excellent solubility in high boiling solvents, favorable color-forming properties, and being capable of giving less deposition, thereby causing less graininess of the resulting image.   A light-sensitive, silver halide, color photographic material having a cyan-colored coupler of the general formula,

United States Patent 1191 Kagami et al.

[ LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CONTAINING CYAN-COLORED COUPLERS [75] Inventors: Teruo Kagami, lruma; Mitsuto Fujiwhara; Takaya Endo, both of Tokyo, all of Japan [73] Assignee: Konishiroku Photo Industry Co.

Ltd.

[22] Filed: July 24, 1972 [21] Appl. No.: 275,211

[30] Foreign Application Priority Data Primary ExaminerJ. Travis Brown Attorney, Agent, or FirmEric l-l. Waters [57] ABSTRACT A light-sensitive, silver halide, color photographic ma- [451 May 21, 1974 terial having a cyan-colored coupler of the general formula,

wherein n is an integer of l to 4; m is an integer of 0 to 2; R is a phenyl group or an alicyclic group, may be used in the form of a solution in an organic solvent which has an automasking mechanism for compensating the drawback in color reproduction of the lightsensitive, silver halide, color photographic material, said cyan-colored coupler having such properties as excellent solubility in high boiling solvents, favorable color-forming properties, and being capable of giving less deposition, thereby causing less graininess of the resulting image. 1

6 Claims,'No Drawings 1 LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPIIIC MATERIAL CONTAINING CYAN-COLORED COUPLERS This invention relates to alight-sensitive, silver ital ide, color photographic material containing a new cyan-colored coupler to be used-in the form of a solution U.S. Pat. No. 3,034,892 discloses compounds of the general formula,

n; CONH(CHz)xQYRz wherein X is an integer of 0 to 4; Y is an. integer. of 0 or 1; R is a group selected from phenyl groups, alkyl groupshaving six to carbon atoms, alkyl-substituted phenyl groups and alkyl-substituted ph'enoxyphenyl groups; and R is a straight chain or branched-chain alkyl group having one tofour carbon atoms, which are known as automasking cyan couplers. The compound (A) of the chemical formula,

CONH(CH1) OQt- 0,1111

tiHu, I

| COCHa 2 pound (A), Japanese Pat. publication No. 29,413/68 discloses compounds of the general formula,

\ CONHR wherein R is a lower alkyl group; and R is a monocyclic aryl group having nine or more carbon atoms and Containing at least one alkoxycarbonyl group. Further, Japanese Pat. publication No. 11,304/67 discloses compounds of the general formula,

' CONHR wherein R is a lower alkyl group, and R is a branchedchain alkyl group having six or more carbon atoms.

The compounds of the above-mentioned general formulas, however, have many drawbacks concerning the efficiency of emulsions as compared with the compound (A). In the case of thecompounds described in Japanese Pat. publication No. 29,413/68, the absorption maximums for masking are present in appropriate spectral region for cyan color image as positive, but the cyan color images formed by color development of a photographic negative are not preferable as negative color images. This is because a photographic positive material matched for said negative is not yet available due to the difficulty of finding a suitable spectral-sensitizing dye for positive color images. Accordingly, color sensitizing dyes suitable for positive color photographic materials are found to cause great difficulties in production techniques. On the other hand, while the coupler compounds described in Japanese Pat. publication No. 1 1,304/67 have less of such drawbacks of spectral absorption as mentioned above, they nevertheless are slow in the formation ofcolor and far lower in'color density than the compound (A), and the resulting dyes are inferior in graininess.

Protect type cyan-colored couplers, which, in view of their natures, are used in negative photographic materials, in general, are desired to have such properties as a high solubility in organic solvents, prominence in automasking effects (broad in width of isosbestic points 'of blue and green portions), favorable color-forming properties andexcellence with respect to graininess of the resulting image, and do not bring about any change in color due to development. Although no coupler having such properties as mentioned above has, of course, been found yet, the compound (A) is a coupler having considerably desirableproperties. It is also well known that naphthol type cyan couplers are lowere in solubility in high boiling solvents by introducing arylazo components therein.

In view of the above, we made extensive studies to find couplers which are not only free from such drawbacks as seen in the compound (A) but also have excellent properties capable of satisfying other characteristics.

The present invention is concerned with lightsensitive silver halide, color photographic materials characterized by containing couplers of the general formula,

O H tsHn wherein n is an integer of l to 4; m is an integer of to 2; R is a phenyl group or an alicyclic group.

In order to substantiate the fact that the couplers used in the present invention are-excellent in solubility in high boiling solvents, the couplers were compared in said solubility with 'a known coupler [the compound (A)]. The results obtained were as set forth in Table 1.

Table 1 Known Compound Exempli- Exempli- Exempli- Coupler (A) fled fled fied coupler l coupler 2 coupler 3 Amount of solvent 8.8 8.5 9.3 required (As the solvent was used tricresyl phosphate, the amount thereof required for dissolving each coupler was expressed in ml.)

Further, a mixture comprising 0.2 g. of each of the abovementioned cyan-colored couplers and 0.8 g. of a cyan coupler was dissolved at 60C. in 1.3 cc. of tricresyl phosphate, and the resulting solution was allowed to stand at normal temperature to measure the period required for deposition of the cyan-colored coupler. The results obtained were'as set forth in Table 2.

Table 2 'caiib'urfd Exempli- Exempli- Exempli- Coupler (A) fied fied fied coupler l coupler 2 coupler 3 Time-required for 3 days 7 days I 6 days 4 days deposition i From the above table, it is understood. that even when used in combination with other cyan couplers, the cyan-colored couplers used in the present invention are excellent in solubility and are less deposited.

Further, the couplers used in the present invention gave favorable results both in their behavior to emulsions and in masking property.

Typical examples of the couplers used in'the present invention are shown below, though these are intended to be representative and non-limiting.

l. l-Hydroxy-4-(2-H-phenylpropionyl-phenylazo)-N- [6-( 2,4-di-t amylphenoxy )butyl I-Z-naphthamide OOCHrCHz- 2. l-Hydroxy-4-( 2-phenylacetyl-phenylazo )-N- 8-( 2,4- di-t-amylphenoxy)butyl]-2-naphthamide M.P. 157-159 C.

Grim

3. l-Hydroxy-4-( 2-cyclohexylcarbonyl-phenylazo)-N- [8-( 2,4-di-t-amylphenoxy )butyl -2-naphthamide M.P. 158-160 C.

amylphenoxy)butyll-Z-naphthamide Procedures for synthesizing the couplers used in the to synthesis examples.

SYNTHESIS EXAMPLE 1 90 Grams of 2'-amin0-3-phenylpropiophenone (m.p. 7273C.), which had been obtained by reducing 2- nitro-3=phenylpropiophenone, was added to a mixed liquid comprising. 1 liter of 10 percent hydrochloric acid, 200 cc. of ethyl alcohol and 200 cc. of dimethylformamide, and the resulting mixture was cooled to i 5C. Into this mixture was dropped with stirring over a period about minutes a mixture comprising 34.5 g. of sodium nitrite and 120 cc. of water, and then the mixture was stirred at 0 i 5C. for about 30 minutes to synthesize a diazo solution. The thus-synthesized diazo solution was dropped, with stirring and cooling to 0 i 5C. over a period of 30 minutes, in a solution of l 85 g. of l-hydroxy-N-[8-(2,4di-tamylphenoxy)butyl]-2-naphthamide in 2.5 liters of pyridine, and the mixed solution was stirred at below 10 C. for 2 hours. Thereafter, the liquid reaction mixture was poured into 8 liters of water to deposit a red precipitate, which was then'washed with water, dried and recrystallized from 2 liters of ethyl alcohol to ob-' tain 240 g. of a red'powder of l-hydroxy-4-(2-B- phenylpropionyl-phenylazo)-N-[8-(2,4-di-tamylphenoxy)but yll-2-naphthamide [the exemplified coupler.( l m.p. l57-l59C., yield 85 percent.

Elementary analysis:

c H N Calculated 77.60 7.50 5.90 Found (7%) 77.63 7.31 5.79

i SYNTHESIS EXAMPLE 2 Synthesis Example 1 was repeated, except that 2'- amino-2-phenylacetophenone (m.p. 9295C.) was used in place of the 2-amino-3-phenylpropiophenone,

SYNTHESIS EXAMPLE 3 In this example was synthesized o-cyclohexylcarbonyl aniline, m.p. 7375 C., yield 35 percent.

Elementary analysis:

c H .N

Calculated (36) 76.81 8.43 6.89 Found (17) 76.6l 8.33 6.78

Subsequently, Synthesis Example l was repeated, except that the said o-cyclohexylcarbonyl aniline was used in place of the 2-amino-3-phenylpropiophenone,

tg pbtain the exemplified coupler (3), mp.

l02-l04C., yield 76 percent.

Elementary analysis:

C H N Calculated 76.60 8.04 6.09 76.78 V8.06 6.3l

Found The present invention is illustrated below by the ,following examples.

EXAMPLE 1 1.0 Gram of the exemplified coupler (l) was completely dissolved at 80C. in a mixed solvent comprising 1 ml. of tricresyl phosphate and 2 ml. of butyl acetate. The resulting solution was mixed with 2 ml. ofa 10 percent aqueous solution of Alkanol B (alkyl-naphthalenesulfonate produced by Du Pont) and with 20 ml. of a 5 percent aqueous gelatin solution, and the resulting mixed solution was subjected to a colloid mill to form a coupler dispersion. The thus formed coupler dispersion was added to ml. of a red-sensitive high speed silver iodobromide emulsion, which was then coated on a film base and dried to prepare a red-sensitive color photographic material.

This color photographic material was exposed to red light through an optical wedge, and then developed at 20C. for 10 minutes with a color developer of the following composition:

N,N-Diethyl-p-aminoaniline sulfate Sodium sulfite Sodium carbonate (monohydrate) Hydroxylamine hydrochloride Potassium bromide Water to make The developedphotographic material was subjected to ordinary stop-fixing, washed with water for 10 to 15 minutes, and then treated for 5 minutes with a bleaching solution of the following composition:

Potassium ferricyanide 100 g. Potassium bromide 50 g. Water to make 1.000 ml.

Subsequently, the photographic material was washed with water for 5 minutes, and then fixed for 5 minutes with a fixing solution of the following composition:

Sodium thiosulfate (pentahydrate) Water to make 250 g. 1,000 ml.

The thus treated photographic material was washed with water for 20 to 25 minutes and then dried to obtain a cyan-colored negative image and a red-positive image composed of unreacted residual coupler. This positive image had a red color sufficient in density, and

the isosbestic points thereof formed masks of 550 mp. .and 440 mu.

EXAMPLE 2 A mixture comprising 1.0 of the exemplified coupler (1) and 3.0 g. of l-hydroxy-N-[6-(2,4-di-tamylphenoxy)butyl]-2-naphthamide was completely dissolved at 80C. in a mixed solvent comprising 4 ml. of tricresyl phosphate and 8 ml. of butyl acetate. The resulting solution was added to 100 parts of a 10 percent aqueous gelatin solution kept at 60C., incorporated with 2 ml. of a 10 percent aqueous Alkanol B solution, and then dispersed by means of a colloid mill to form a coupler dispersion. The thus-formed coupler dispersion was added to 100" ml. of a red-sensitive high speed silver iodobromide emulsion, which was then treated in the same manner as in Example 1 to prepare a red-sensitive color photographic material.

According to the same procedure as in Example 1, the color photographic material was exposed to red light through an optical wedge, color-developed, fixed,

water-washed, bleached and then fixed to obtain a cyan-colored negative image simultaneously with an excellent red-positive image.

EXAMPLE 3 Example 2 was repeated, except that di-n-butyl phthalate was used in place of the tricresyl phosphate, to prepare a red-sensitive color photographic material. This photographic material was exposed to red light, and then treated in the same manner as in Example 2 to obtain a cyan-colored negative image simultaneously with an excellent red-positive image.

EXAMPLE 4 wherein n is an integer of l to 4; m is an integer of 0 to 2; and R is a phenyl group or an alicyclic group.

2. A light-sensitive, silver halide, color photographic material as claimed in claim 1, wherein said coupler is included in the red-sensitive gelatinous silver halide emulsion layer.

3. A light-sensitive, silver halide, color photographic material as claimed in claim 1, wherein the photographic material comprises a red-sensitive silver halide emulsion layer containing the coupler of the formula of claim 1, together with a blue-sensitive silver halide emulsion layer containing a yellow coupler and a green-sensitive silver halide emulsion layer containing a magenta coupler.

4. A light-sensitive, silver halide, color photographic material as claimedin claim 1, wherein the coupler is a compound of the said general formula in which R is phenyl group.

5. A light-sensitive, silver halide, color photographic material as claimed in claim'l, wherein the coupler is a compound of the said general formula in which R is a chlorophenyl, alkylphenyl or alkoxyphenyl group.

6. A light-sensitive, silver halide, color photographic material as claimed in claim 1, wherein the coupler is a compound of the said general formula in which R is cyclohexyl group. 

2. A light-sensitive, silver halide, color photographic material as claimed in claim 1, wherein said coupler is included in the red-sensitive gelatinous silver halide emulsion layer.
 3. A light-sensitive, silver halide, color photographic material as claimed in claim 1, wherein the photographic material comprises a red-sensitive silver halide emulsion layer containing the coupler of the formula of claim 1, together with a blue-sensitive silver halide emulsion layer containing a yellow coupler and a green-sensitive silver halide emulsion layer containing a magenta coupler.
 4. A light-sensitive, silver halide, color photographic material as claimed in claim 1, wherein the coupler is a compound of the said general formula in which R is phenyl group.
 5. A light-sensitive, silver halide, color photographic material as claimed in claim 1, wherein the coupler is a compound of the said general formula in which R is a chlorophenyl, alkylphenyl or alkoxyphenyl group.
 6. A light-sensitive, silver halide, color photographic material as claimed in claim 1, wherein the coupler is a compound of the said general formula in which R is cyclohexyl group. 